EP0109779A1 - Copolymère d'éthylène - Google Patents

Copolymère d'éthylène Download PDF

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Publication number
EP0109779A1
EP0109779A1 EP83306484A EP83306484A EP0109779A1 EP 0109779 A1 EP0109779 A1 EP 0109779A1 EP 83306484 A EP83306484 A EP 83306484A EP 83306484 A EP83306484 A EP 83306484A EP 0109779 A1 EP0109779 A1 EP 0109779A1
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Prior art keywords
copolymer
melting point
branching
ethylene copolymer
ethylene
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German (de)
English (en)
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EP0109779B1 (fr
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Masaki Kohyama
Masanori Motooka
Takashi Ueda
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Mitsui Chemicals Inc
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Mitsui Petrochemical Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond

Definitions

  • This invention relates to ethylene/C 4 -C 20 ⁇ -olefin copolymers which have new characteristics in composition distribution, degree of branching, randomness and crystallinity by DSC melting point and are not described in the prior literature. These copolymers have excellent transparency, impact strength, tear strength, blocking resistance, environmental stress cracking resistance, heat resistance and low-temperature heat sealability.
  • this invention relates to an ethylene . copolymer having the following characteristics (A) to (I).
  • HP-LDPE Low-density polyethylene obtained by the high-pressure process has been extensively used as films, hollow containers, injection-molded articles, pipes, steel pipe coatings, cable and wire coatings, foamed articles, etc. because of its pliability and relatively good transparency.
  • HP-LDPE has poor impact strength, tear strength and environmental stress cracking resistance (to be sometimes abbreviated as ESCR), it is not suitable for use in fields which require materials which are excellent in these properties and have the aforesaid good properties in a well balanced combination.
  • low-density polyethylenes obtained by copolymerizing ethylene with a olefins having at least 3 carbon atoms under medium to low pressure conditions have better mechanical strength, ESCR and transparency than HP-LDPE, and therefore attract interest as a substitute of HP-LDPE.in some applications.
  • the mechanical strength and optical properties of L-LDPE are still required to be improved, and it still does not have satisfactory heat sealability.
  • L-LDPE cannot meet the recent requirement for high strength which arises from the higher speeds of packaging machines such as bag-making machines and filling and packing machines or the reduced thickness of packing materials. It has therefore been desired to develop materials which are excellent in these properties and at the same time have the inherent good properties mentioned above in a well balanced combination.
  • British Patent No. 2,093,047 pertains to an improvement in the blocking resistance of an ethylene copolymer.
  • the ethylene copolymer disclosed there has a single DSC melting point, and its heat resistance and low-temperature heat sealability are not well balanced. It has been found that an attempt to improve low-temperature heat sealability results in reduced heat resistance, and an attempt to improve heat resistance, on the other hand, ends in deteriorating low-temperature heat-sealability.
  • British Patent No. 2,093,044 proposes an ethylene/a-olefin copolymer having a specified long chain branching index and a specified short chain branching distribution. Because this copolymer has a broad composition distribution, its composition distribution characteristics are not satisfactory. Its transparency and impact strength are also unsatisfactory. Hence, this copolymer cannot provide a material having excellent properties in a well balanced combination.
  • U.S. Patent No. 3,645,992 discloses a continuous process for producing a uniform, random, partially crystalline ethylene/a-olefin copolymer having a narrow distribution of molecular weight by using a vanadium-type catalyst.
  • This ethylene copolymer also has a single DSC melting point, and cannot have heat resistance and low-temperature heat sealability in a well balanced combination.
  • the present inventors have extensively worked on the development of an ethylene copolymer which has excellent mechanical properties, optical properties, blocking resistance, heat resistance and low-temperature heat sealability in a well balanced combination.
  • the ethylene copolymer of this invention is defined by the characteristics (A) to (I) which will be described below in detail.
  • the ethylene copolymer of this invention has a melt flow rate (MFR) of from 0.01 to 200 g/10 min., preferably from 0.05 to 150 g/10 min. [characteristic (A)).
  • the MFR is measured in accordance with ASTM D1238E. If the MFR exceeds 200 g/10 min., the ethylene copolymer has poor moldability and mechanical strength. If it is less than 0.01 g/10 min., its moldability is also deteriorated undesirably.
  • the ethylene copolymer of this invention has a density of from 0.900.to 0.945 g/cm 3 , preferably 0.910 to 0.940 g/cm (characteristic (B)].
  • the density is measured in accordance with ASTM D1505. If the density exceeds 0.945, the transparency, tear strength, impact strength and low-temperature heat sealability of the copolymer are deteriorated, and if it is less than 0.900 g/cm 3 , the antiblocking property of the copolymer becomes poor.
  • the ethylene copolymer of this invention has a composition distribution parameter (U), defined by the following equation wherein Cw represents a weight average degree of branching and Cn represents a number average degree of branching, of not more than 50, for example O ⁇ U ⁇ 50, preferably not more than 40, more preferably not more than 30 [characteristic (C)]..
  • U composition distribution parameter
  • U- is a parameter showing the distribution of components of the copolymer which is irrelevant to its molecular weight.
  • characteristics (D), (E), (F), (G), etc. to be described below it is an important characteristic which specifies the structure of the copolymer of this invention. If U exceeds 50, the composition distribution of the copolymer is too broad, and the copolymer has poor transparency, tear strength, impact strength, blocking resistance and low-temperature heat sealability. Hence, it is difficult to provide the desired excellent properties in a well balanced combination.
  • Cw and Cn used in equation (1) for calculating U are determined by the following method.
  • the copolymer (10 g) is added to about 2 liters of a mixture of p-xylene and butyl cellosolve (80:20 by volume) and the mixture is heated at about 130 °C in the presence of 2,5-di-tert.butyl-4-methylphenol (0.1% by weight based on copolymer) as a heat stabilizer. Then, about 1 kg of diatomaceous earth (tradename Celite #560, made by Johns-Manville Company, U. S. A.) was added to the resulting solution, and the mixture was cooled to room temperature with stirring. This operation results in coating the copolymer on diatomaceous earth.
  • diatomaceous earth tradename Celite #560, made by Johns-Manville Company, U. S. A.
  • the entire mixture is filled in a jacketed cylindrical column (diameter about 3 cm) which is set perpendicularly. While the column is maintained at a temperature of 30 °C, a solvent having the same composition as the above mixed solvent in the same volume as a solution flowing from the bottom of the column is passed (about 1 liter/hr) through the column from its top. The solution flowing out from the bottom of the column is collected in a receiver. To the collected solution is added methanol in an amount twice the volume of the collected solution to precipitate the eluted copolymer. After confirming that upon addition of methanol, the copolymer no longer precipitates, the.flowing of the solution is stopped.
  • the temperature of the column is then raised to 35 °C, and the flowing of the solution and the passing of the mixed solvent are resumed and continued until the copolymer no longer flows out.
  • the foregoing operation is carried out at intervals of 5 °C until the operation is finally carried out at 120 °C.
  • the copolymer fractions precipitated from methanol are separated by filtration and dried to obtain fractions.
  • the weight of each of the fractions is then measured, and the degree of branching per 1000 carbons of each of the fractions is determined by the 13C-NMR method shown below with regard to the characteristic (D).
  • the amount of components having a degree of branching of not more than 2/1000 carbons is not more than 15% by-weight, for example 15 to 0% by weight, preferably not more than 10% by weight, more preferably not more than 7% by weight [characteristic (D)].
  • the characteristic (D) is a parameter which means that the amount of components which have too a small degree of branches bonded to the main chain of the copolymer is small.
  • the composition distribution parameter (C) it is an important characteristic which together with the composition distribution parameter (U), specifies the structure of the ethylene copolymer of this invention. If the copolymer contains more than 15% by weight of components having a degree of branching of not more than 2/1000 C, it has poor transparency, tear strength, impact strength, and low-temperature heat sealability, and it is difficult to provide the desired excellent properties in a well balanced combination.
  • the degree of branching denotes the number of branches per 1000 carbons.in the copolymer chain, and is determined in accordance with the method disclosed in G. J. Ray, P. E. Johnson and J. R. Knox, Macromolecules, 10, 773 (1977) from the area intensity of a signal of methylenic carbon adjacent to a branch observed by the 13 C-NMR spectrum.
  • the comonomers are a copolymer of butene-1 and 4-methylpentene-l
  • the positions of the chemical shifts of the signals assigned to the above methylenic carbons are respectively 33.8 ppm and 34.5 ppm with TMS (tetramethylsilane) as a standard.
  • the amount of components having a degree of branching of at least 30/1000 carbons is not more than 15% by weight, for example 15 to 0% by weight, preferably not more than 13% by weight, more preferably not more than 7% by weight. [characteristic (E)].
  • the characteristic (E) is a parameter which means that the amount of components having a main chain structure in which the number of branches bonded to the main chain of the copolymer is too large is small.
  • the composition distribution parameter (C) and the branching degree condition (D) it is an important characteristic which together with the composition distribution parameter U and the branching degree condition (C), specifies the structure of the copolymer of this invention. If the amount of components having at least 30 branches/1000 C exceeds 15% by weight, the copolymer has deteriorated antiblocking property and tends to soil an object with which it makes contact.
  • the amounts of components having not more than 2 branches/1000 carbons and components having at least 30 branches/1000 carbons are determined as follows:-The relation between the cumulative weight fractions and the degrees of branching obtained from the fractionation of the copolymer performed in determining U with regard to the characteristic (C) is plotted on a graph, and the points corresponding to two-branches/1000 C and 30 branches/1000 C on the graph are interpolated, and the cumulative weight fractions corresponding to these points are determined based on the results, the above amounts can be determined.
  • the average chain length ratio of methylene groups is not more than 2.0, for example 2.0 to 1.0, preferably 1.7 to 1.0, more preferably 1.5 to 1.0 [characteristic (F)].
  • the average chain length ratio in characteristic (F) is a parameter which shows the random structure of ethylene and the a-olefin in the molecular chains of the copolymer, and is one of the important characteristics which together with the characteristics (C) to (E), specifies the structure of the ethylene copolymer of this invention. If the average chain length ratio of methylene groups exceeds 2.0, the copolymer has inferior transparency, tear strength, impact strength, blocking resistance and low-temperature heat-sealability, and it is difficult to provide the desired excellent properties in a well balanced combination.
  • the average chain length ratio of methylene groups in characteristic (F) is determined from the average methylene chain length calculated by using 13 C-NMR and the average block methylene chain length calculated by excluding the case where the number of methylene groups between two adjacent branches is not more than 6, and defined as the ratio of the average block methylene chain length to the average methylene.chain length.
  • the block methylene chain length is the number of methylene groups between branches determined from the signals of the third and fourth and subsequent methylenic carbons observed when the number of methylene groups between branches is at least 7.
  • the positions of the chemical shifts of the signals assigned to the third and fourth and subsequent methylenes are 30.1 ppm and 29.6 ppm,_ respectively, with TMS as a standard.
  • DSC differential scanning calorimeter
  • T 1 in the characteristic (G) is less than (175 x d - 46)°C (d is as defined above), the copolymer has reduced heat resistance. If T 1 is higher than 125°C, the transparency and low-temperature heat sealability of the copolymer are inferior. When T 1 - T n is higher than 18°C or T 1 - T 2 exceeds 5°C, the tear strength, impact strength and low-temperature heat sealability of the copolymer are deteriorated, and it is difficult to provide the desired excellent properties in a well balanced combination.
  • the DSC melting points in characteristic (G) and the amount of heat of crystal fusion (H 1 ) and the amount of heat of crystal fusion (H T ) are measured and determined by the following methods.
  • FIGS. 1 and 2 accompanying this application are charts showing examples of DSC endothermic curves of the ethylene copolymers of this invention.
  • T 1 in Figure 1 appearing as a peak on the highest temperature side or as a shoulder or T 1 in Figure 2 (the intersecting point of tangential lines drawn at the deflection point P 1 on the high temperature side of the shoulder and the deflection point P 2 on the low temperature side of the shoulder) is the highest melting point (T 1 ).
  • T 1 a plurality of DSC points are designated as T 1 , T 2 , ....T n from the high temperature side to the low temperature side.
  • T 2 is thus the second highest melting point
  • T n is the lowest melting point.
  • the amount of heat of a portion defined by the straight line connecting the points at.60°C and 130°C of the endothermic curve (the base line A-A' in the drawings) and the endothermic curve between them is defined as the total amount of heat of crystal fusion (H T ).
  • the ratio of the amount of heat of crystal fusion (H 1 as defined above) at the highest melting point (T 1 ) among the DSC melting points (n melting points; nZ3) to the total amount of heat of crystal fusion (H T as defined above) is 0 ⁇ H 1 ⁇ T T ⁇ 0.40, preferably 0.01 ⁇ H 1 /T T ⁇ 0.35 (characteristic (H)].
  • the ratio of the amounts of heat of fusion, H I /T T , in the characteristic (H) is related to the crystallinity characteristics by DSC melting points of the ethylene copolymer of this invention together with the characteristic (G). If the H l /H T ratio exceeds 0.40, the tear strength, impact strength and low-temperature heat sealability of the copolymer are deteriorated.
  • this characteristic (H) serves to provide the desired excellent properties of the copolymer of this invention in a well balanced combination.
  • the ethylene copolymer of this invention is a copolymer of ethylene with an ⁇ -olefin having 4 to 20 carbon atoms, preferably 6 to 18 carbon atoms. At least one a-olefin may be used.
  • the ⁇ -olefin are 1-butene, 1-pentene, 1-hexene, 4-methyl-l-pentene, 1-heptene, 1-octene, 1-decene, 1-tetradecene, 1-octadecene, and mixtures of these.
  • propylene i.e. C 3 4-olefin
  • the resulting copolymer has poor tear strength, impact strength and environmental stress cracking resistance.
  • the ethylene copolymer of this invention additionally has the following characteristic (J).
  • the copolymer has an n-decane-soluble content at 23°C of not more than 8% by weight, for example 8 to 0% by weight, preferably not more than 5% by weight, more preferably not more than 3% by weight, especially preferably not more than 2% by weight.
  • the copolymer of this invention which additionally has the characteristic (J) has higher blocking resistance and is not likely to soil an object with which it makes contact.
  • n-decane-soluble content is determined as follows:
  • the copolymer of this invention can be produced, for example, by copolymerizing ethylene with at least one C 4 -C 20 ⁇ -olefin in the presence of a catalyst composition composed of
  • the highly active solid component (a-I) is a component which can by itself be used as a highly active titanium catalyst component, and is well known.
  • the component (a-1) can be obtained by reacting a magnesium compound and a titanium compound with or without an auxiliary reagent so as to obtain a solid component having a high specific surface area.
  • the solid component (a-1) has a specific surface area of at least about 50 m 2 /g, for example about 50 to about 1000 m 2 /g, and preferably about 80 to about 900 m 2 /g.
  • the solid component (a-1) contains about 0.2 to about 18% by weight, preferably about 0.3 to about 15% by weight, of titanium, and has a halogen/titanium atomic ratio of from about 4 to about 300, preferably from about 5 to about 200, and a magnesium/titanium atomic ratio of from about 1.8 to about 200, preferably from about 2 to about 120.
  • the component (a-1) may contain other elements, metals, functional groups, electron donors, etc. in addition to the essential ingredients.
  • aluminum and silicon may be used as the other elements and metals.
  • the functional groups are alkoxy and aryloxy groups.
  • the electron donors are ethers, carboxylic acids, esters and ketones.
  • One preferred example of the method of producing the solid conpcnent (a-I) is a method which comprises treating a complex of a magnesjum halide and an alcchol with an organic metal compound, for example an organoaluminum compound such as a trialkylalununum or an alkyl aluminum halide, and reacting the treated product with a titanium compound. The details of this method are described in the specification of U.S. Patent No. 4,071,674, for example.
  • the alcohol (a-2) used to treat the highly active solid component (a-1) may be an aliphatic, alicyclic or aromatic alcohol which may have a substituent such as an alkoxy group.
  • the alcohol are methanol, ethanol, n-propanol, iso-propanol, tert-butanol, n-hexanol, n-octanol, 2-ethylhexanol, n-decanol, oleyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, isopropylbenzyl alcohol, cumyl alcohol and methoxyethanol.
  • Aliphatic alcohols having 1 to 18 carbon atoms are especially.preferred.
  • Treatment with the alcohol is preferably carried out in an inert hydrocarbon such as hexane and heptane.
  • an inert hydrocarbon such as hexane and heptane.
  • the reaction conditions can be properly selected depending upon the kind of the alcohol.
  • the reaction can be carried out at a temperature of about -20 to about +150oC, preferably about -10 to about +100°C, for several minutes to about 10 hours, preferably about 10 minutes to about 5 hours.
  • the alcohol (a-2) is taken in the form of an alcohol and/or alkoxy group in the solid component (a-1).
  • the amount of the alcohol (a-2) so taken into the component (a-1) is 4 to 100 moles, especially 5 to 50 moles, per titanium atom.
  • a part of titanium is sometimes liberated from the solid component (a-1).
  • the resulting titanium catalyst component is preferably well washed with an inert solvent after the reaction, and then used for the polymerization.
  • the organoaiuminum compound component (b) to be used together with the titanium component (a) is typically a compound of the general formula R n AlX 3-n (wherein R represents a hydrocarbon group, for example a C 1 -C 15 alkyl group or a C 2 -C 8 alkenyl group, X represents a halogen atom, and 0 ⁇ n ⁇ 3).
  • halogen compound component (c) When the halogen compound component (c) is not used, it is desirable to use the component (b) so that in its general formula, n is preferably 1.5 to 2.0, more preferably from 1.5 to 1.8 as an average composition.
  • the halogen compound component (c) is, for example, a halogenated hydrocarbon such as ethyl chloride or isopropyl chloride, or silicon tetrachloride which can act as a halogenating agent for the component (b).
  • a halogenated hydrocarbon such as ethyl chloride or isopropyl chloride, or silicon tetrachloride which can act as a halogenating agent for the component (b).
  • its amount is preferably such that the total amount of the halogens in the components (b) and (c) is from 0.5 to 2 atoms, particularly from 1 to 1,5 atoms, per aluminum atom in the component (b).
  • the copolymerization of ethylene with the C 4 -C 20 ⁇ -olefin can be carried out in the liquid or vapor phase in the presence of the catalyst composition composed of components (a), (b) and (c) described above in the presence or absence of an inert diluent such as an inert hydrocarbon at a temperature of, for example, 0 to about 300°C.
  • an inert diluent such as an inert hydrocarbon
  • the desired ethylene copolymer can be easily obtained by performing the copolymerization in the presence of an inert hydrocarbon under conditions in which the resulting ethylene copolymer dissolves, at a temperature of, for example, about 120 to 300°C, preferably about 130 to 250°C.
  • the ratio between ethylene and the C 4 -C 20 ⁇ -olefin can be properly selected. Preferably they are used in such proportions that the mole ratio of ethylene/C 4 -C 20 ⁇ -olefin in the resulting ethylene copolymer becomes _about 99:1 to 90:10.
  • the amount of the titanium catalyst component (a) used is, for example, about 0.0005 to about 1 millimole/liter, preferably about 0.001 to about 0.1 mole/liter, calculated as titanium atom.
  • the amount of the organoaluminum compound (b) is that which serves to maintain polymerization activity. Desirably, it is used so that the Al/Ti atomic ratio becomes from about 1 to about 2,000, preferably from about 10 to about 500.
  • the polymerization pressure is generally atmospheric pressure to about 100 kg/cm , especially about 2 to about 50 kg/cm.
  • the ethylene copolymers of this invention have better transparency, impact strength, tear strength, blocking resistance, low-temperature heat sealability, heat resistance and ESCR than not only HP-LDPE but also conventional L-LDPE, and retain these excellent properties in a well balanced combination. Accordingly, they are especially suitable for use as packaging films.
  • These copolymers can be processed into various articles such as films, containers, pipes, tubes and household goods by various molding methods such as T-die molding, inflation film molding, blow molding, injection molding and extrusion.
  • Various types of composite films can be formed by extrusion coating on other films or by coextrusion. They can also be used as steel pipe coatings, cable coatings or foamed articles.
  • copolymers of this invention may be used as blends with other thermoplastic resins, for example polyolefins such as HP-LDPE, medium-density polyethylene, high-density polyethylene, polypropylene, poly-I-butene, pbly-4-methyl-1-pentene, ethylene/propylene or 1-butene copolymers which have low crystallinity or are amorphous, and propylene/1-butene copolymer. It is also possible to incorporate petroleum resins, waxes, heat stabilizers, weather stabilizers, antistatic agents, antiblocking agents, slip agents, nucleating agents, pigments, dyes, inorganic or organic fillers, synthetic rubbers, natural rubbers, etc. into the copolymers of this invention.
  • polyolefins such as HP-LDPE, medium-density polyethylene, high-density polyethylene, polypropylene, poly-I-butene, pbly-4-methyl-1-pentene, ethylene
  • Ethanol 50 millimoles was added at room temperature to 50 millimoles, at Ti, of the component (A-1) suspended in refined hexane. The temperature was raised to 50°C, and they were reacted at this temperature for 1.5 hours. After the reaction, the solid portion was repeatedly washed with refined hexane.
  • the resulting catalyst component (B-l) had the following composition.
  • a 200-liter continuous polymerization reactor was continuously charged with 100 liters/hr of dehydrated and refined hexane, 7 millimoles/hr of diethyl aluminum chloride, 14 millimoles/hr of ethyl aluminum sesquichloride, and 0.6 millimole/hr, as Ti, of the catalyst component (A-1) prepared as above.
  • Ethylene (13 kg/hr), 4-methyl-l-pentene (19 kg/hr) and hydrogen (45 liters/hr) were simultaneously fed continuously into the polymerization vessel, and the monomers were copolymerized at a polymerization temperature of 165 o C and a total pressure of 30 kg/cm 2 for a residence time of 1 hpur under such conditions that the concentration of the copolymer in the hexane solvent was maintained at 130 g/liter.
  • the catalytic activity corresponded to 21,700 g of copolymer/mmole of Ti.
  • the resulting copolymer was formed into a film having a width of 350 mm and a thickness of 30 p by a commercial tubular film forming machine (made by Modern Machinery Company) for high-pressure polyethylene.
  • the molding conditions were as follows:-
  • the film was evaluated by the following methods.
  • the copolymer obtained in this example had inferior transparency, blocking resistance and low-temperature heat sealability because its composition distribution was considerably broad and it contained much components having high crystallinity and low crystallinity.
  • Hexane dehydrated and purified (0.8 liter) and 0.2 liter of 4-methyl-l-pentene were fed into a 2-liter autoclave. After the inside of the autoclave was fully purged with nitrogen, 2.0 millimoles of triethyl aluminum and 0.02 millimole calculated as Ti atom of the Ti.catalyst used in Comparative Examples land 2 were added. Then, hydrogen under 0.6 kg/cm 2 was introduced, and the pressure was elevated with ethylene (2.5 kg/cm2). The monomers were copolymerized at a polymerization temperature of 70°C for 2 hours to give 295 g of a copolymer. The catalytic activity corresponded to 14,800 g of the copolymer/mmole of Ti.
  • the copolymer obtained in this example had poor low-temperature heat sealability because its composition distribution was very broad, and it shows a single melting point at 124.5°C.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Organic Insulating Materials (AREA)
EP83306484A 1982-10-25 1983-10-25 Copolymère d'éthylène Expired EP0109779B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83306484T ATE24323T1 (de) 1982-10-25 1983-10-25 Ethylencopolymer.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP186043/82 1982-10-25
JP57186043A JPS5975910A (ja) 1982-10-25 1982-10-25 エチレン共重合体

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EP0109779A1 true EP0109779A1 (fr) 1984-05-30
EP0109779B1 EP0109779B1 (fr) 1986-12-17

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EP83306485A Expired - Lifetime EP0107967B2 (fr) 1982-10-25 1983-10-25 Composition de catalyseur et son application dans la polymérisation ou copolymérisation d'oléfines
EP83306484A Expired EP0109779B1 (fr) 1982-10-25 1983-10-25 Copolymère d'éthylène

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US (1) US4525469A (fr)
EP (2) EP0107967B2 (fr)
JP (1) JPS5975910A (fr)
AT (2) ATE20591T1 (fr)
CA (2) CA1206466A (fr)
DE (2) DE3364388D1 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0286177A1 (fr) * 1987-04-06 1988-10-12 Dsm N.V. Copolymère d'éthylène
EP0341091A2 (fr) * 1988-05-06 1989-11-08 The Dow Chemical Company Polyéthylène linéaire à densité ultra basse
EP0436520A1 (fr) * 1990-01-03 1991-07-10 Gas Research Institute Tuyau en polyéthylène de longue vie pour la distribution de gaz
EP0444606A1 (fr) * 1990-02-27 1991-09-04 Mitsui Petrochemical Industries, Ltd. Copolymère éthylène/pentène-1, procédé pour sa préparation et composition à base de copolymère éthylène/pentène-1
EP0450304A2 (fr) * 1990-02-27 1991-10-09 Mitsui Petrochemical Industries, Ltd. Copolymères de l'éthylène et du pentène-1 et leur procédé de préparation
US5091353A (en) * 1984-03-16 1992-02-25 Mitsui Petrochemical Industries, Ltd. Process for producing ethylene copolymer
EP0495099A1 (fr) * 1988-12-26 1992-07-22 Mitsui Petrochemical Industries, Ltd. Copolymeres olefines et leur production
US5218071A (en) * 1988-12-26 1993-06-08 Mitsui Petrochemical Industries, Ltd. Ethylene random copolymers
US5336746A (en) * 1988-12-26 1994-08-09 Mitsui Petrochemical Industries, Ltd. Propylene random copolymers and processes for preparing same
US5639842A (en) * 1988-12-26 1997-06-17 Mitsui Petrochemical Industries, Ltd. Ethylene random copolymers
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EP0630916A2 (fr) * 1990-02-27 1994-12-28 Mitsui Petrochemical Industries, Ltd. Copolymères de l'éthylène et du peinture, leur procédé de préparation et compositions de copolymères de l'éthylène et du pentène
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EP0444606A1 (fr) * 1990-02-27 1991-09-04 Mitsui Petrochemical Industries, Ltd. Copolymère éthylène/pentène-1, procédé pour sa préparation et composition à base de copolymère éthylène/pentène-1
WO2007061587A1 (fr) 2005-11-23 2007-05-31 Dow Global Technologies Inc. Interpolymeres heterogenes a base d'alpha olefine d'ethylene en composition a phase separee

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CA1217899A (fr) 1987-02-10
EP0107967B2 (fr) 1993-04-07
JPS5975910A (ja) 1984-04-28
EP0109779B1 (fr) 1986-12-17
DE3368420D1 (en) 1987-01-29
DE3364388D1 (en) 1986-08-07
ATE20591T1 (de) 1986-07-15
JPH0339093B2 (fr) 1991-06-12
ATE24323T1 (de) 1987-01-15
US4525469A (en) 1985-06-25
CA1206466A (fr) 1986-06-24
EP0107967B1 (fr) 1986-07-02
EP0107967A1 (fr) 1984-05-09

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